Process for flameproofing polymeric materials



United States Patent 3,516,853 PROCESS FOR FLAMEPROOFING POLYMERIC MATERIALS Giuliana C. Tesoro, Dobbs Ferry, N.Y., and Wing-Kai Lee, Hackensack, and Kelvin B. Domovs, Newark, N.J., assignors to J. P. Stevens & Co., Inc., New York, N.Y., a corporation of Delaware No Drawing. Continuation-impart of application Ser. No. 490,658, Sept. 27, 1965. This application Oct. 17, 1967, Ser. No. 675,789 Claims priority, application G/rzgt Britain, Feb. 21, 1967,

Int. Cl. C09d /18; D06m 13/44 U.S. Cl. 117-136 13 Claims ABSTRACT OF THE DISCLOSURE A method for fiameproofing polymeric material through treating said material with a solution of tris(1-aziridinyl) phosphine oxide and a nitrogen containing phosphonate, and cellulosic material impregnated with the insoluble product formed by co-reactiong tris(1-aziridinyl) phosphine oxide and a nitrogen containing phosphonate.

-(a) R is selected from the group consisting of hydrogen and lower alkyl having from 1 to 4 carbon atoms;

(b) Q is a grouping, being one selected from the formulae consisting of x"- on 3,516,853 Patented June 23, 1970 ice where:

n has a value of 0 t0 2;

R and R" are selected from the group consisting of hydrogen, lower alkyl, halogen, and lower haloalkyl;

X is a grouping of the formula (NH)aN Riv where:

d, R', and R are as defined below; X" is selected from the group consisting of halogen,

OR R

Ii/ li/ P\ P R OR Riv where:

dhas a value of 0 to 1;

R and R are selected from the group consisting of hydrogen, alkyl, hydroxyalkyl, alkoxyalkyl, poly(alkyleneamino)alkyl, poly(alkyleneoxy)alkyl, aminoalkyl,

akanoyl, alkoxycarbonyl 1 (hydroxyalkoxy)carbonyl [f)O-AOH] A is an alkylene group (divalent, saturated and aliphatic) (hydroxymethyl)carbamoyl [ff-IIL-CHzOH] bis (hydroxymethyl) carbamoyl C-N(CHOH)2 a 1 alkylcarbamoyl ET? alkyl(hydroxymethyl)carbamoyl -CN-G a $11,011]

wherein G is a saturated alkyl group having 1-5 carbon amidino (hydroxymethyl) amidino) Tl-III- C H2 0 H bis (hydroxymethyl) amidino [(3N(-CH2OH)2 phospinylidyne [E P O] and (R"'+R can form a heterocyclic ring of which the nitrogen atom is also a member;

() Y is selected from the group consisting of X and where R and X' are as defined above;

((1) Y is a group of the formula and a grouping of the formula 0 i 110); on CH- where n, R, R, R", and X" are as defined above.

The aforedescribed phosphonates can be used in formulations for treatment of polymeric materials, including films and textile fibers, in order to impart thereto such useful properties as durable fiame retardation and enhanced dyeability. A particularly desirable property of many of these phosphonates is their solubility in aqueous media.

The phosphonates of this invention may be prepared by reacting halogenated phosphonates with nitrogenous compounds such as ammonia, primary amines, secondary amines, hydrazine, urea, and guanidine, thereby replacing at least some of the halogen atoms with amino, substituted amino, hydrazino H NNH,, ureido H NCONH, and guanidino H NC(=NH)NH groupings.

The substituted ureas, hydroxyalkyl carbamates, other carbamates, and other amides (such as result respectively from reaction of isocyanates, cyclic carbonates, esters of chloroformic acid, and acyl chlorides on amino phosphonates) can be converted to reactive N-( hydroxymethyl) derivatives, also soluble in aqueous media, by treatment with formaldehyde, paraformaldehyd-e, or other formaldehyde precursor.

Representative of the halogenated phosphonates which are useful starting materials for the preparation of nitrogenated phosphonates of this invention are the following compounds:

The halogenated phosphonate starting material may first, if desired, be modified by reaction with trialkyl phosphites before subsequent reaction with appropriate nitrogen-containing compounds. Such preliminary phosphonation yields halophosphonates which, because of their higher phosphorus content, possess enhanced flame retardation characteristics. Thus, for example, bis(2-chloroethyl) (2-chloroethyl)phosphonate may be reacted with a trialkyl phosphite according to the following equation:

Equation 1 ll (ClCH2OHzO)zP CH2CHzOl+(R O);P

In the equation given above, R represents a substituted or unsubstituted aliphatic radical, including branched or straight-chain alkyl, haloalkyl, or alkenyl.

The nitrogen compounds which can be reacted with the halogenated phosphonates to obtain water-soluble reactive nitrogen-containing phosphonates include ammonia, aliphatic primary amines, substituted and unsubstituted hydrazines, alkylenediamines such as ethylenediamine; hydroxyalkyl alkylenediamines, such as 2- (2 aminoethylamino)ethanol; hydroxyalkylamines such as 2 aminoethanol; cyclic amines such as morpholine and pyrrolidine; cyclic diamines such as piperazine; alkylenimines such as ethylenimine and Z-methylaziridine; amides such as urea; and amidines such as guanidine. The resulting substituted ureas and guanidines can be methylolated by means of formaldehyde to form additional valuable water-soluble reactive amido and amidino phosphonates.

Useful products can be obtained by employing any one of a large number of amino compounds, and the examples listed previously are merely illustrative of the nitrogenous compounds which can be used to prepare the novel nitrogen-containing phosphonates.

Preferred products are obtained by reacting the halogenated phosphonates with ammonia; with hydrazine; with alkylenediamines having the formula NH C H NH where a has a value of from 2 to 6; and with alkylenimines having the formula CH-R Hz where R is hydrogen or lower alkyl having from 1 to 4 carbon atoms. In these preferred products, the amino groups introduced are highly reactive, and are therefore capable of entering into polymerization and crosslinking reactions with suitably selected co-reactant-s. Furthermore, the equivalent weight of the nitrogen-containing radical is low, and the proportionate phosphorus content of the product accordingly high. This is desirable in compounds designed to impart flame-retardant properties, since the effectiveness of the compounds employed as flame retardants is generally proportional to their phosphorus content.

Preferred products also are obtained by reacting halogenated phosphonates with alkylamines such as methylamine, dodecylamine, and octadecylamine, with secondary amines such as 2,2-iminodiethanol, with amidines such as guanidino H NC( NH)NH- and by ureido H NCONH groups, respectively.

The conversion of the halogenated phosphonates to the corresponding nitrogen-containing phosphonates in accordance with this invention is suprisingly achieved without significant aminolysis of the ester groups, and the reaction can be represented schematically by the following Equations 2 and 3 wherein a simple chloroethyl phosphonate, namely, bis(2-chloroethyl) (2-chloroethyl)phosphonate is used as an example of a suitable starting material.

Employing the procedure of this invention, partial replacement of the halogen atoms is possible, with the number of amino groups introduced being dependent upon the reaction conditions, including the ratio of amine to halogen compound used, the time and temperature of the reaction, the concentration of reactants and the solvent. In addition, different nitrogen compounds can simultaneously be employed in the steps represented by Equations 2 and 3, yielding products containing difiYerent nitrogenous residues in the same molecule. When it is desirable to replace every halogen with an amino group, a rapid reaction rate is preferred, whereas a slower rate is preferred for partial replacement of the halogen groups. The ratio of amino compound can be varied from about 0.2 mole to about 5 moles per halogen atom present in the starting material, with the preferred ratio ranging from 0.5 to 2. Although the solvent used is not critical, alcohols, glycols and glycol ethers are generally preferred since they are particularly effective solvents for the starting materials. Ethylene glycol is a particularly desirable solvent and appears to have an accelerating efiect on the desired reaction. Water can also be used, but care must be exercised in avoiding hydrolysis of the haloalkyl groups present by using carefully controlled conditions of temperature and pH, avoiding a temperature higher than about 80 C. and a pH lower than about 6.0. In carrying out the reaction in organic solvents, temperatures of 50 C. to 150 C. are preferred, but temperatures outside this range can also be employed. At temperatures below 50 C. reaction takes place very slowly, but nevertheless at an appreciable rate with some amino compounds. At temperatures of from 150 C. to about 200 0., reaction proceeds rapidly at atmospheric or superatmospheric pressure, depending upon the boiling point of the reactants. 'However, reaction at temperatures greater than 150 C. is usually accompanied by discoloration of the reaction mixture.

Generally, the extent of reaction at any given time can be determined by withdrawing a representative sample of the reaction mixture, and titrating the ionic halide present argentometrically. The percentage of the total halide present in ionic form is a measure of the extent of reaction. The extent of reaction can also be assessed by testing the water solubility of the reaction mixture, since the conversion of halophosphonate to nitrogen-containing phosphonate is accompanied by an increase in water solubility. When the desired extent of reaction has been reached, the product can be isolated by any of several methods. It is generally desirable to neutralize the halogen acid formed either during the reaction or upon its completion by adding an inorganic base such as alkali carbonate or bicarbonate. The alkali halide formed in this neutralization can be filtered if desired. The solvent and any residual unreacted nitrogenous compound can then be stripped by distillation at atmospheric pressure or in vacuo. Alternatively, if purification of the product is not required, water may be added to dissolve the alkali halide formed upon neutralization, and the solution may be used directly. The nitrogen-containing phosphonates of this invention, in general, possess the desirable feature of water solubility and can therefore be applied in aqueous solutions.

It is also within the scope of this invention to prepare the nitrogen-containing phosphonates described hereinabove by reacting a phosphonate represented by generic Formulae C and D (a) Q is a grouping, being one selected from the formulae consisting of -P u fill l CH H (c) Z is one selected from the group consisting of YI', Q!

and

inabove with one compound selected from the group consisting of pho horus oxychloride, an alkyl isocyanate, a cyclic carbon te, chloroformic acid esters and acyl chlorides.

The phosphoramidation of an amino phosphonate is graphically represented as follows:

wherein J represents one valence of the non-nitrogenous moiety of a phosphonate represented by either C or D. R is as defined hereinabove. It will be observed that EPO replaces H at the amino sites on the phosphonates. These compounds are classified as phosphoramidesipolyphosphonates.

This reaction is illustrated in Equation 4 where an amine reaction product obtained by replacing the halogens of bis(2 chloroethyl)(2-chl0roethyl)phosphonate with ethylenediamine.

Equation 4 lustrated by Equation 7, wherein G, J, and R' are as previously defined.

Formula 9 Formula 9 represents derivatives in which alkoxycarbonyl,

-COG

J) replaces H at amino sites of amino polyphosphonates. The resulting alkyl carbamates are alkoxyformamido polyphosphonates.

The reaction of phosphorus-containing amines represented by generic Formula C or D with acyl chlorides is illustrated in Equation 8 using an alkanoyl chloride,

ll [(HzNCHzCHzNHCHaCHzO)gP CHzCHzNHCHzCHzNHkP 0 Formula 6 It is apparent from the example shown in Equation 4, that the ratio of polyamine to POCl can be varied, to form products of varying molecular weight and containing varying ratios of phosphonate to phosphoramide groupings in the same molecule. By the use of this reaction, starting with the phosphorus-containing polyamines of the present invention, further new products can be obtained and the physicochemical properties can be further varied.

The reaction of phosphorus-containing amines having the structure of C or D with an alkyl isocyanate,

O=C=N-G is illustrated as follows:

Equation 5 JNH+O=C=NG JNCN-G R!!! Bl!!! 1!]:

Amino Alkyl Formula 7 Polyphosphonate Isocyanate Formula 7 denotes derivatives in which alkylcarbam- Y C-NG All

replaces H at amino sites of amino polyphosphonates. The resulting substituted ureas are substituted ureido polyphosphonates.

The reaction of phosphorus-containing amines represented by C or D with a cyclic carbonate is illustrated by the following reaction with ethylene carbonate.

Formula 8 denotes a derivative having a (hydroxyalkoxy) carbonyl grouping I JOAOH replacing H at amino sites of the amino polyphosphonate. The resulting hydroxyalkyl carbamate is a (hydroxyalkoxy) formamido polyphosphonate.

The reaction of phosphorus-containing amines represented by C or D with esters of chloroformic acid is il- G and R being as previously defined.

Equation 8 JNH+C1CG .TNCG

ll I II R! O R!!! 0 Formula 10 Formula 10 represents derivatives in which alkanoyl,

replaces H at amino sites of amino polyphosphonates. The resulting amides are alkanamido polyphosphonates.

Attention is directed to particular case of Equations 2 and 3 above when d is zero, R is H, and R' is either amidino,

(ClCH2CHzO)zPO HzCHzCl Formula 11 Equation 10 Formula 11 2 HzN-CNH2 Ila Formula 12 The analogous particular equations using urea are as follows. (Note that is urea when d is zero, R is H, and R' is carbamoyl.)

Accordingly, by means of the types of reactions illus trated by Equations 9 and 10, halogenated phosphonates can be converted to guanidino phosphonates. Likewise, referring to Equations 11 and 12, halogenated phosphonates can be converted to ureido phosphonates. Partial replacement of the halogen atoms by guanidino or ureido is possible as was noted in connection with amino groups, the principles being similar to those explained following Equation 3.

As had been noted in the discussion of nitrogen compounds operable as reactants to obtain water-soluble phosphonates (after Equation 1), substituted guanidines and ureas made by means of halogenated phosphonates can be methylolated. For instance, several such hydroxymethyl derivatives can be formed from the ureido phosphonate represented by Formula 13. In order to simplify the following equations,

Equation 15 Formula 13 E O CHzOH Formula 19 Tris (hydroxyruethyl) compound Hence, several degrees of methylolation are possible, depending on the mole ratio of formaldehyde (or its precursor) to ureido phosphonate.

Other amides of this invention can be methylolated, a process which generally increases solubility in water and results in a more reactive agent for treating cellulosic films, fibrous assemblies, and textile materials. In connection with acylation reactions illustrated above by Equations 5, 6, 7, and 8, amides of this invention were formed which likewise can be modified by reaction with formaldehyde in the process called methylolation. In the following equations, G and J are as previously defined.

Equation 16 When R' is H in Formulas 7 and 20, then a similar reaction can result in the formation of an isomer, Formula 21, as well:

Equation 17 H-If-fi-lf-G H0110 HOCHz-lTI-(f-IIF-O o H J H Formula 21 Equation 18 shows the type of bis(hydroxymethyl) derivative resulting when the molar ratio of formaldehyde is doubled:

Similarly, when R' is H in Formulae 8, 9, and 10, then the following types of groupings result by methylolation:

From Formula 8:

HOCI-IzCH2O-CNJ Formula 23 From Formula 9:

GOCNJ 0 HQOH Formula 24 From Formula 10:

G(H3N-J' O H2OH Formula 25 The nitrogen-containing phosphonates obtained according to the processes outlined above find many useful applications, either as prepared, viz. in soluble form, or in crosslinked form resulting from reaction with polyfunctional compounds. Thus, the phosphonates can be employed to impart flame-retardant properties to a variety of organic substrates. Such substrates are generally polymeric films or fibrous assemblies. Of particular interest are those substrates containing cellulose in the form of paper, cotton, regenerated cellulose, cellophane and the like. If the treated substrate is not to be exposed to washing or other wet handling, the phosphonates can be used without a co-reactant. If the treated substrate is to be wet-treated, as for example, in the case of a textile fabric, then the phosphonate can be insolubilized in situ by reaction with a co-reactant.

The phosphonates of this invention can also be used to enhance the dyeability of polymeric materials. Thus, for example, these phosphonates can be employed to modify the dyeability of hydrophobic fibers, if desired. The ability to enhance dyeability is utilized to best advantage in treating polymers which are compatible with the phosphonates, e.g., polyolefins and other hydrophobic, chemically inert polymers. The phosphonate compound is added before forming or shaping of the polymer in order to provide modified polymers of improved polarity and dyeability. Amounts of nitrogencontaining phosphonates between about 1% and about 12% based on the weight of the polymer being modified provide products having excellent dyeability. If utilized before shaping of the polymer, the nitrogen-containing phosphonates are added in solution. However, the phosphonates can be insolubilized by treating the modified polymer with polyfunctional compounds after the shaping, molding, spinning, or other forming operation. Phosphonates of generic Formulae A and B wherein R and/or R are alkyl groups having more than 8 carbon atoms are of particular advantage in providing enhanced dyeability to polymeric materials.

In the treatment of cellulosic fabrics for either enhancing their dyeability or their flame-resistant characteristic, it is convenient to use the polymethylol derivatives in the form of the neutralized aqueous reaction solution resulting from the polymethylolation reaction. The padding of the solution mixture onto the cellulosic fabric is done so as to impregnate the fabric with 2 to 20% of the reagent, based on the weight of cellulose in the fabric. Also, between approximately 8 and 80 parts by weight of magnesium chloride, zinc tetrafluoroborate, or similar acid-generating compound should be used in the pad bath per 100 parts by weight of the polymethylolated derivative. (Mineral acid salts of ammonia and amines, or organic acids are also operable as suitable catalysts.) The padded fabric is dried at a moderate temperature, e.g., 50 to 70 C., then cured for about 3 to 6 minutes at a high temperature, preferably higher than about 100 C. Temperatures in the range of 120 to 200 C. yield excellent results, although higher temperatures may be employed.

The phosphorus-containing nitrogenated compounds obtained according to the process outlined above, illustrated in Equation 4, react readily with polyfunctional compounds to form crosslinked phosphorus-containing resins. This insolubilization reaction is generally caused by heating, and the catalysts for the insolubilization reactions are determined by the structure of the co-reactants. For example, a textile material, and particularly a textile material comprising cellulosic fibers, can be treated with an aqueous solution of a polyamino phosphonate and a suitable co-reactant, dried and heated (cured) to insolubilize the phosphorus-containing nitrogenated compounds in situ, thereby obtaining a flame-retardant finish durable to laundering and dry cleaning. Among the nitrogenated phosphonates of the present invention, those containing aziridinyl groups (obtained by reaction of haloalkyl phosphonates with alkylenimines) can be insolubilized either in vitro or in situ even Without the addition of a co-reactant, yielding crosslinked polyamine resins of high phosphorus content.

Suitable co-reactants for the insolubilization of the nitrogenated phosphonates of this invention are generally those containing at least two groupings reactive toward active hydrogen atoms, and particularly toward the amino hydrogen atoms present in the nitrogenated phosphonates.

Among such groupings are, for example, epoxy groupings (-OH-CH2) o aziridinyl groupings CH-R \CI-I2 and activated vinyl groupings such as, vinylsulfonyl SO CH =CH (mg, in divinyl sulfone), acrylamido -NCOCH=CH (e.g., in 1,3,5 triacryloyl hexahydro s triazine), and acryloyl -COCH=CH (e.g., in diacryloyl-hexane). The preferred co-reactants include formaldehyde, tetrakis-(hy droxymethyl)phosphonium halides, polyepoxides (polyglycidyl ethers of polyols, such as are available from the Shell Chemical Company, under the trade name Eponite), polyaziridinyl compounds such as tris(1-aziridinyl) phosphine oxide, tris(2 methyl 1 aziridinyl) phosphine oxide, polyhalides such as polyepihalohydrins, polyhalophosphonates, and the like, monomeric and oligomeric phosphonitrilic halides and similar reactive compounds.

Methylolated compounds of this invention undergo an acid-catalyzed insolubilization reaction without the necessity for co-reactants. This valuable property makes it possible to insolubilize such N (hydroxymethyl) derivatives of amido phosphonates in situ on a textile material.

In the presence of an acid or acid-generating salt, such as magnesium chloride, zinc nitrate, or zinc tetrafluoroborate, hydroxy methyl groups undergo a condensation reaction with hydroxy groups, which results in insoluble derivatives of high molecular Weight. Using Formula 25 for purposes of illustration, the following type of condensation occurs with a polymer such as cellulose (one reacted site of which is denoted by HO-Cell):

Equation 19 Inasmuch as J represents but one valence of several valences in the non-nitrogenous moiety of a polyphosphonate, it is apparent that macromolecules of cellulose are crosslinked by such a reaction.

Similarly, polymethylolated derivatives of phosphonates of this invention can be insolubilized either in vitro or in situ without the addition of a co-reactant. The following type of acid-catalyzed reaction occurs, yielding resins of high P content.

Equation 20 When the formation of the crosslinked products heretofore described is carried out on textile materials, and particularly on cellulosic textiles, the textile is usually impregnated with a solution of the monomers, preferably an aqueous solution. The concentration of monomers required, of course, depends upon the type of textile material and upon the properties to be effected. For optimum durability of flame-retardant properties on cellulosic fabrics, solutions containing from about 10% to about 30% total reactants by input, are satisfactory. When a cO-reactant for the polyamino phosphonate is used, the ratio of polyamino phosphonate to co-reactant can be varied according to the identity of the co-reactant. Thus, for example, when the co-reactant is tris(1-aziridinyl)-phosphine oxide, ratios of 3:1 to 1:3 of polyamino phosphonate to tris(l-aziridinyl)phosphine oxide are preferred. The pH of the textile treating solution may range from about 5 to about 10. After treating with the monomer solution, the textile is dried and heated (cured) to effect insolubilization. Heating at temperatures above C. is generally desirable in order to accelerate the reaction with a heating cycle of from 2 to 20 minutes at C. to C. being preferred. After heating, the treated textile is washed to remove residual soluble compounds. Cellulosic textiles treated in this manner do not support combustion, and this property is unimpaired even after 100 launderings. Moreover, the tensile strength of the treated cellulosic textile is not significantly reduced. It is also worthy of note that the solubility and excellent chemical compatibility of the polyamino phosphonates make it possible to apply these flame-retardant finishes in conjunction with other finishing agents, such as softeners.

In the examples which follow, all parts given are by Weight unless otherwise indicated.

The test results reported were obtained according to (b) Preparation of the following test methods: 0 CH3 0 Vertical flame resistanceAATCC 34-1952 (in inches). C1OH CH Q1 O C|,H 0( JH (OCH CH CD, Ellipse flame resistance-ADR 53, 812 (1964) (in mm.) p p 7 'rStiffnessCantilever procedureASTM D-1388-55T H2NCH2H2NHH2m 0H3 CHQCHZNHCHZCH2NH2 The preparation was repeated as in part (2) with the Tensile $tTehgth-R3-Ve1 Strip methdASTM exception that 24.0 parts of ethylenediamine were used.

59T After 12 hours reaction at reflux temperature, the reaction T al StrengthASTM D1414-63 product was isolated in the same manner as in part (a) Abrasion resistance%toll flex abrader-Z lbs. head, d f h l i ifi ti f ll d b argenlbs. toggle. A TM D117561T y tometric titration) of the water-soluble solid isolated, the Crease Y (angle measured amination of the chloro groups in the halogenated phosiIl degreis, total of p and filling directions, phonate was 80.0% complete, calculated on the basis of LaunderingAamples laundered in automatic home-type th amount of ethylenediamine u ed.

agitator washing machine at 140 F. for the full cycle, 15 (c) The preparation was repeated as in part (a) with 5-lb. load. |Samples flat-bed pressed. the exception that 4.8 parts of ethylenediamine were used. Alkaline scouring--Samples heated at 95 C. in an aque- The reaction product remained water-insoluble during the ous solution containing 2 g./l. sodium carbonate and course of reaction. After 8 hours at reflux temperature, 5 g./l. detergent. Fabric: liquor ratio 1:50. The scoured the reaction product was recovered in the same manner as samples neutralized in dilute acetic acid solution, rinsed in part (a). The analysis (saponification followed by thoroughly in water and dried. argentometric titration) of the water-insoluble product Damage due to retained chlorineAATCC92-1962 isolated indicated that 1 out of the 5 chloro groups in the (percent strength lost). halogenated phosphonate was aminated.

EXAMPLE 2 EXAMPLE 1 O Preparation of a polyamino phosphonate by amination of Armnation of the halophosphonate of Formula 3 with the halophosphonate f Formula 3 with ethylenedi.

ethylenediamine amine (a) Preparation of Into a three-necked flask equipped with a stirrer, a

In to a three-necked flask equipped with a mechanical thermomcteh a reflux condenser a dropping funnfil stirrer a thermometer, a reflux condenser and a dropping were charged 90 parts of ethylenediamme d1ssolved 1n funnel were charged 48.1 parts of ethylenediamine dis- 50 parts of ethylene glycol solution 183 parts solved in 50 parts of isopropyl alcohol. Into the stirred of the halogenated phosphonate m 50 parts of ethylene glycol were added over a period of one-half hour. The solut1on kept at 25 parts of the halogenated 4.0 reaction was exothermic and the temperature was main- Phosphonate dissolved in 50 parts of isopropyl alcohol tained at 110 to 115 C. with occasional cooling. Samples wfire added Period of 1 1 The reaction was were withdrawn periodically for the argentornetric desllghfly e p- After the addltlon was completed, termination of ionic chloride. The amination leveled off the reaction SOllltlOI'l was heated slowly to reflux (85 (3.). at ompletion in 1 hour The final product may be Samples were withdrawn periodically for the argenrepresented by the formula n i 1 ii HzNCHzOHzNHCHrOHrOP-O-fiJH-h-O CHP(OCHzCHzNHCHgCHgNHz):

HzNCHzOHgNHCHzCHa 0H hCHrCHzNHOHzCHzNHz tometric determination of ionic chloride formed and for The reaction mixture was cooled to h then the determination of water solubility. The reaction prod- 25 of WatPr and 120 P51rts of aqueous sodlhm uct became completely Water s01ub1e in 4 hours and droxrde solution were added. The resulting solut1on could from the ionic chloride determination, the amination was 55 dlhlted to any h h cohcehtrahoh and employed 100% complete in 9 hours. The reaction product was wlthout further Punficatmh' then cooled to 30 to 35 C., and 200' parts of isopropyl EXAMPLE 3 alcohol, 55.2 parts of potassium carbonate and 10.0 parts Water were added to the viscous solution. The mixture was stirred at 30 to 35 C. for several hours and, after Preparation of a polyamino phosphonate by amination of the halophosphonate of Formula 3 with aqueous amstanding overnight, was filtered to separate the inorganic moma salt precipitated. The solvent was distilled under vacuo to a three-necked flask equipped with a mechanical at 90 C. from the homogeneous filtrate, and the product stirrer, a thermomfiter, a reflux condenser and a pp was recovered as a yellowish solid residue. Argentomeflhhel Parts of 2 ammonium hydroXide and 50.0 parts of isopropyl alcohol were charged. Into the stirred solution kept at 25 C., 97.7 parts of the halogenated phosphonate dissolved in 50 parts isopropyl alcohol were added over a period of 1 hour. The reaction was slightly exothermic. Samples were withdrawn periodically for the argentometric determination of ionic chloride tric titration of the water-soluble product showed that it still contained 5.6% ionic chloride. The bound chlorine content was 1.31%, determined by saponification followed by argentometric titration. This corresponded to 96.5% completion of the amination reaction of the chloro grohpshl the halogenated phosphonate? on the bas1s of formed and for the determination of water solubility. The the Weight of recovered P the Yleld of the ahhha reaction mixture was kept at 35 to 40 for 8 hours and tlOIl was Elemental analysis Of the product isolated was lowly heated to 85 C and kept at this temperature showed the polyamino phosphonate contained 10.39% until no further increase of ionic chloride formation. The

P, 12.80% N. reaction mixture turned completely water-soluble in 10 15 hours. The reaction product was recovered in the same manner as shown in Example 1. The analysis (saponification followed by argentometric titration) of the watersoluble viscous product indicated that the amination of the chloro groups was 90% complete. The final product may be represented by the formula Preparation of a polyaziridinyl phosphonate by amination of the halophosphonate of Formula 3 with ethylenimine Into a three-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a dropping funnel were charged 550 parts potassium bicarbonate and 610 parts of the halogenated phosphonate dissolved in 300 parts of ethyl alcohol. To the solution, kept at 25 to 30 C., 242 parts of ethylenimine were added over a period of 1 hour. The reaction Was slightly exothermic. The reaction solution was then gently heated to 55 C. and kept at this temperature. After 26 hours, the inorganic salt and the excess of the inorganic base precipitated were filtered off. The solvent was then distilled off under vacuo at 25 to 30 C. Analysis (saponification followed by argentometric titration) of the water-soluble viscous residual product showed the amination of the chloro groups was 92% complete. The final product may be represented by the formula:

H 0 C CH2 Nomcmol ..CE l OiH l(OCH.OH.N y H2O H2O Ha GH2 2 NOE: Hz H2 H2O OCH2OH2N Determination of the aziridinyl content by the method of Schaefer (Journal American Chemical Society 77,

lowed by argentometric titration) of the water-soluble product showed the amination of the chloro groups in the halogenated phosphonate was 78% complete. The final product may be represented by the formula Preparation of a polyamino phosphonate by amination with ethylenediamine of the product resulting from the action of triethyl phosphite on the halophosphonate of Formula 3 Into a three-necked flask equipped with a stirrer, a thermometer, a reflux condenser were charged 305.3 parts of the halogenated phosphonate and 830.0 parts of triethyl phosphite. The reaction mixture was heated to reflux at 145 to 150 C. for 40 hours. The excess triethyl phosphite was then distilled off under vacuo at 95 C. and analysis of the water-insoluble viscous reaction product showed that 60% of the chloro groups in the halogenated phosphonate had been replaced with diethyl phosphonate radi cals.

Two hundred parts of the product prepared as described above were aminated with parts of ethylenediamine in the same manner as described in Example 1. After 24 hours at reflux temperature, the reaction product was isolated in the same manner as in Example 1. The analysis (saponification followed by argentometric titration) of the recovered water-soluble solid product indicated that 75% of the chloro groups present in the rearranged product had been aminated. The final product may be represented by the formula 0 I! H (1? CH3 0 OOH2CH2P(OCH2CH3)3 HzNCHzCHzNHCHzCHgOP-OCHPO--JJHP (CHaCH2 )2P CH2 H2 H3 OCHzCHzNHOHzOHzNH;

CHzGHzfKO 011201193 5918-6922, 1955) gave an aziridinyl equivalent weight of EXAMPLE 7 132.0 compared with a calculated value of 128.5 for the halogenated phosphonate wherein every chlorine has been replaced with an aziridinyl group,

EXAMPLE 5 Preparation of a polyaziridinyl phosphonate by animation of the halophosphonate of Formula 3 with 2-methylaziridine Into a three-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a dropping funnel were charged 16.6 parts of potassium carbonate and 24.4 parts of the halogenated phosphonate dissolved in 100 parts of isopropyl alcohol. Into the stirred solution, kept at 25 to 30 C., 13.7 parts of 2-methylaziridine dissolved in 100 parts of isopropyl alcohol were added over a period of one-half hour. The reaction mixture was then heated to 85 C. and maintained at this temperature. After 22 hours,

the inorganic salt and the excess of inorganic base precipitated were separated and the solvent was distilled 011 under vacuo at 30 to 35 C. Analysis (saponification fol- Preparation of phosphoramide derivative of a polyamino phosphonate by amidation with phosphorus oxychloride Into a three-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a dropping funnel were charged 50 parts of the polyamino phosphonate prepared according to Example 3 and parts of water. Into the stirred solution, kept at 5-10 C., 3.0 parts phosphorus oxychloride, dissolved in 50 parts benzene, were added. The reaction mixture was stirred at 10 C. for 3 hours and the organic layer was separated and discarded. The aqueous layer was then stripped under vacuo and further neutralized with potassium carbonate in isopropyl alcohol to liberate the free organic base of the phosphoramide derivative which was still completely water-soluble. Elemental analysis of the derivative prepared showed a 13.2% phosphorus content compared with the 11.6% phosphorus content of the polyamino phosphonate of Example 3.

EXAMPLE 8 Preparation of epoxy derivative of a polyamino phosphonate by etherification with epichlorohydrin Into a three-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a dropping funnel were charged 100 parts of the polyarnino phosphonate prepared in Example 3. To the solution, kept at 24 to 30 C., 28.0 parts of epichlorohydrin were added and the solution was stirred for another 2 hours. Into the homogeneous solution 30.6 parts of triethylamine were added over a period of 1 hour and the mixture was stirred for another 5 hours. The precipitate formed during this time was filtered off. This by-product (7.3 parts) was found to be triethylamine hydrochloride. The solvent was then distilled off under vacuo at room temperature and a viscous liquid was recovered. Analysis (hydrochlorination with aqueous magnesium chloride) showed the product had an oxirane oxygen content of 0.84% corresponding to 0.53 milliequivalent of epoxy groups per gram of product.

EXAMPLE 9 Preparation of a polyarnino phosphonate by amination of bis(2-chloroethyl) (2-chloroethyl) phosphonate with ethylenediamine Into a reaction flask containing 6.0 parts of bis(2-chloroethyl) (2-chloroethyl) phosphonate and 2.6 parts of dimethyl sultoxide kept at 25 C. with occasional cooling were added slowly 1.8 parts of ethylenediamine. Samples were withdrawn periodically for the determination of ionic halide argentometrically. The amination leveled off at 83.5% completion in 168 hours at 25 C., as determined from the ionic chloride titration. The final product may be represented by the formula:

EXAMPLE l Gelation of a polyarnino phosphonate with tris(1- aziridinyl) phosphine oxide and with a polyepoxide The polyarnino phosphonate prepared as described in Example 1 was reacted with tris(1-aziridinyl) phosphine oxide and with a polyepoxide composed of poly(2,3- epoxypropyl) ethers of polyols (Eponite 100, product of Shell Chemical Co.). This gelation experiment consisted of weighing into a Weighing dish varying amounts of either the polyaziridine or the polyepoxide with 1.0 gram of the polyarnino phosphonate by using methanol-water mixture as diluent. The dish with its contents was first heated in an oven at 80 C. for 20 minutes to evaporate the diluent and was then cured at 110 to 120 C. in a forced draft oven for 20 minutes. The glass-like gels formed were rinsed three successive times with 25 grams of water each time. The washed resin was then separated by filtration and the solid was dried in an oven at 150 C. to constant weight. The weight diiference before and after gelation (with the subsequent washing and drying) was taken to measure the percent yield of insoluble polymer formed from the two co-reactants. The following results were obtained:

Parts of tris (l-aziridinyl) phosphine Percent Parts of Eponite 100 per part of Polyamino Phosphonate 18 EXAMPLE 11 Gelation of a polyarnino phosphonate with tris(laziridinyl) phosphine oxide and with a polyepoxide The polyarnino phosphonate prepared as described in Example 3 was gelled with tris(1-aziridinyl) phosphine oxide and with a polyepoxide (Eponite according to the procedure described in Example 10. The following results were obtained:

Parts of tris (l-aziridinyl) phosphine Percent oxide per part of yield of polyarnino insoluble phosphonate polymer Parts of Eponite 100 per part of Polyamino Phosphonate EXAMPLE 12 Gelation of a polyaziridinyl phosphonate with tris(1- aziridinyl) phosphine oxide, formaldehyde, and tetrakis (hydroxymethyl) phosphonium chloride HONATE WITH AND WITHOUT ZINC TETRAFLUO- ROBORATE AS THE CATALKST Percent Zn (BF4)2 Percent based on the weight yield 01' of polyaziridinyl insoluble phosphonate polymer (ii) GELATIN OF POLYAZIRIDINYL PHOSPHONATE WITH TRIS(1-AZIRIDINYL) PHOSPHINE OXIDE Part of tris (l-aziridinyl) phosphine oxide Percent per part of polyyield of aziridinyl insoluble phosphonate polymer (iii) GELATIN OF PO'LYAZIRIDINYL PHOSPHONATE WITH TETRAKIS(HYDROXYMETHYL)PHOS-PHONIUM CHLORIDE (THPC) Percent Part of 'IHPC per yield of part 01 polyariziriinsoluble dinyl phosphonate polymer (iv) GELATIN OF POLYAZI'RIDINYL PHOSPHONATE WITH FORMALIN Part of formaldehyde Percent per part of polyyield of aziridinyl phosinsoluble phenate polymer 19 'EXAMPLE 13 Part of trls (l-azirldinyl) phosphine Percent oxide per part of yield of polyamlno insoluble phosphonate polymer polyaziridine; 0.2% non-ionic wetting agent was added to the treating solution.

Before the treatment the fabric samples were dried at 105 C. and weighed in an analytical balance. The weighed samples were then treated with the reagent solution using a laboratory padder and setting the rolls at such a pressure as to give wet pickup. The fabric samples so treated were framed to original dimensions and dried in a forced draft oven at C. for 15 minutes, then cured at 135 C. for 15 minutes. After curing the samples were neutralized in dilute acetic acid solution, washed in a non-ionic detergent solution at 60 to 70 C., then dried at C. and weighed on an analytical balance to determine the weight gain (W.G.) resulting from 15 the treatment. The following results were obtained:

Percent P Percent N Wt. ratio Percent total produe reagent Calcd. Celcd.

of Ex. 1 applied Percent from rem to APO OWF 1 W.G. Found W.G. Found W.G.

OWF=based on weight of fabric treated.

The properties of the treated samples were as follows:

Cr. recov. Stifiness Char length (W and Tensile warp in vertical F str., ft.- Tear str., (face), flame test Sample degrees lbs. ft.-lbs. mg./cm 1 inches 71 6. 2 940 2 B EL 1 Sum of angles for warp (W) and filling (F) directions. 2 BEL: Burned Entire Length.

EXAMPLE 14 Samples of cotton twill fabric (weight 8 oz./sq. yd.) were treated with a formulation comprising varying The treated samples were exposed to incremental alkaline scouring and the scouring was followed by flame retardancy tests and elemental analysis. The results obtained were as follows:

Percent P and percent N ratios of the product 'of Example 1 and tris(l-aziridinyl) phosphine (APO) oxide. The pH of the aqueous solu- 65 tion of the product of the Example 1 was adjusted to 9 by adding sodium hydroxide before the addition of the EXAMPLE 15 Example 14 was repeated and the treated samples were exposed to multiple laundering at 60 to 70 C. in a home-type Washing machine. The following results were obtained:

Wt. fiatit Percent total P pro uc reagen ercent P Percent of Ex 1 applied Percent N to APO OWF W.G Found Calod. Found Calcd.

Sample A 1:1 21.0 18. 0 2.08 2. 30 2. 73 3.26 B 1:1 19. 2 l5. 5 1. 54 2. 03 2. 37 2. 87

21 The treated samples were laundered and the effect of laundering was followed by flame retardancy tests and elemental analysis. The following results were obtained:

22 EXAMPLE 17 Example 14 was repeated, but instead of the product of Example 1, the product of Example 3 was used in combination with tris(1-aziridinyl)phosphine oxide in a 1:1 weight ratio. The results were as follows:

Retained Percent total after 50L,

reag. Percent P Percent N percent applied Percent OWF W.G. Found Oalcd. Found Calcd. P N

Sample Char length in vert.

f fg ggg 15 The treated samples were exposed to incremental alkaline scouring with the following results: 0 10 30 50 Found Retd. Found Retd.

Char length in inches in vert. flame test Sample A Sample B Hours of scour:

Other propertles of the treated fabric were compared 4.8 3.5 with those of the untreated control initially and after 50L if 2:; (50 launderings) with the following results: i P and I; 52 4. 5

2 hours of scour- Sample Untreated Found- A B control Crease recovery (W and F) 240 253 152 Percent Shrinkage after 50L: 97

F 1.5 1.0 2.5 0 Tensile strength F Orig J 67 66 79 32 50L 62 65 03 1. 47 Tear strength (F).

Orig 2.0 3.5 7.4 72

Found 500 200 850 525 375 500 35 P 1.25 Percent damage due to retained chlo1-ine 1 10 6 1. 64 Stiffness (W):

Orig 2, 290 630 946 68 50L 910 805 966 80 It is apparent that the treatment described in this example imparts to the cotton excellent flame retardant prop- The h Si 1 t f S 1 B f n I erties durable to 50L. The crease recovery of the fabric P Y 6 Proper 0 p 6 were as 0 and its dimensional stability are greatly improved and no chlorine damage is noted. The decrease in tear strength and abrasion resistance can be partially or wholly com- Untreated pensated by after treatment with suitable lubricants such length Inches (meal test) Sample B control as polyethylene emulsions, cationic softeners and the like without impairing other desirable properties.

EXAMPLE 16 Crease Recovery (degrees W and Example 14 was repeated but instead of the product Pel'cgntshrinkage after 5 5 0f EXflmPIe 1, the Pmduct of Example 2 was used in FI:I:I:I:III:IIIIIIIIIIIII: 2:0 2:5 combination with tris(l-aziridinyDphosphine oxide in a figg f g m F 1 60 79 1:1 weight ratio. The following results were obtained: After 5011::I:1:111:11:11:11:: e0 93 Tear Strength, F: Percent Char length in vert. flame test r m 7 4 t ta1reag. P t applied OWF W G Orlg- Aftel 30 originalfliul n 150 850 S fiAfter ggL 300 500 1. 1.2 3.2 4.0 M 1 2 i 5 0 4. 8 Orlglnal 1, 790 940 121 11, BEL Afml'floL 1,193 966 The physical properties of the treated samples were as follows:

Tensile Tear Flex Stifi- EXAMPLE 18 Sample strenght,F strength,F abrasion,W ness,W

76 3 4 215 1 443 Example 14 was repeated, but the product of Example 67 225 4 was used without any co-reactant in the presence and 74 225 639 in the absenc of Zn BF catal st. Untreated control 74 6.6 850 040 e y Char length in ellipse flame Percent Percent test, hours of scour Reag. Catalyst Curing Wt. OWF OWF Conditions Gain 0 2 5 8 Sample A.-. 23.4 C.,15M1n 14.7 7.7 11.3 15.0 16.0 B 22.8 1.6 160 0.,15 Mi.u. 14.9 5.3 11.0 14.3 20.3

23 EXAMPLE 19 Example 14 was repeated using the product of Example 4 in combination with tris(l-aziridinyl)phosphine oxide (APO). The following results were obtained:

24 under vacuum to recover a very viscous liquid. Analysis (saponification followed by argentometric titration) of the water-soluble viscous product indicated that the ami- The treated samples were exposed to incremental alkaline scouring with the following results:

Sample Char length in inches in vert. flame test A B Hours of scour:

0 5. 0 4. 0 4. 1 5. 1 3. 9 4. 7 5. 2 3. 9 4. 7 8 5. 2 4. 0 4. 7 Percent P and Percent N:

2 Hours of scour:

Found:

1.90 2.60 Percent Retained 91 66 93 90 5 Hours of scour:

Foun

P 1.57 1. 94 1.84 2.58 Percent Retained 92 64 90 89 8 Hours of scour:

oun

1.80 2.39 Percent Retained EXAMPLE Example 14 was repeated but instead of the product of Example 1, the product of Example 6 was used in combination with tris(l-aziridinyDphosphine oxide in a 1:1 weight ratio. The results were as follows:

Char length in inches vertical flame nation of the chloro groups was 98% complete. The final product may be represented by the formula (H) CH3 vO EXAMPLE 22 Preparation of a polyfibis-(2-hydroxyethylamino)]phosphonate by amination of the halophosphonate of Formula 3 with 2,2-iminodiethanol Into a three-necked flask equipped with a mechanical stirrer, a thermometer, a reflux condenser, a dropping funnel were charged 525.7 g. (5.00 moles) of 2,2'-iminodiethanol, 550.0 g. (5.5 moles) of potassium bicarbonate and 100 g. of 2-propanol. Into the stirred mixture, kept at 25 C., 610.5 g. (1.0 mole) of the halogenated phosphonate dissolved in 400 g. of 2-propanol was added drop wise. No exotherm was observed during addition. After addition, the reaction mixture was heated gradually to reflux at 85 C. Samples were withdrawn periodically for argentometric determination of chloride ion formation. The amination was halted in hours time when no further increase of ionic chloride formation Was observed.

The potassium chloride formed during the amination was filtered off and the 2-propanol and water were stripped 011 under vacuum to recover a very viscous Percent total Percent test, hours of scour liquid. Analysis (saponification followed by argentometric g lfig $22 3 0 2 5 8 titration) of the water-soluble product indicated that the 19 9 11 5 4 2 5 6 5 3 7 0 45 amination at the chloro sites was 95% complete. The

' final product may be represented by the formula H H CH3 (fi/O CH2CH2N(CH2CH2OH)2 (HOCHzCH-z) zNCHzCHzOP-O CH-P-O H-P (HOCH2CH2)2NCH2 H2 H OCHzCH2N(CHzCH2OH)z OOHzCHzNflJHzCHzOH):

EXAMPLE 21 EXAMPLE 23 Preparation of a polyamino phosphonate by amination of the halophosphonate of Formula 3 with methylamine Into a three-necked flask equipped with a mechanical stirrer, a thermometer, a reflux condenser, a dropping funnel and a gas inlet tube were charged 200 g. of 2-propanol. Methylamine gas was bubbled into the alcohol at room temperature for 15 minutes. Then 610.5 g. (1.00 mole) of the halogenated phosphonate dissolved in 800 g. of 2-propanol were added dropwise to the amine-saturated solution while maintaining the flow of amine gas. The reaction was slightly exothermic and the temperature was kept at to C. After the addition was completed, the reaction mixture was heatedgradually to reflux at C. Samples of the reaction mixture were withdrawn periodically for the argentometric determination of ionic chloride. The amination was halted in 60 hours when no further increase of ionic chloride formation was observed.

The methylamine hydrochloride formed during reaction was filtered off and the 2-propanol was then stripped 01$ Preparation of a polyhydrazino phosphonate by amination of the halophosphonate of Formula 3 with hydrazine Into a three-necked flask equipped with a mechanical stirrer, a thermometer, a reflux condenser and a dropping funnel were charged 33.6 g. of hydrazine (1.0 mole) dissolved in 100.0 g. of 2-propanol. Into the stirred solution kept at 25 C. was added dropwise 122.1 g. (0.2 mole) of the halogenated phosphonate dissolved in 150.0 g. of 2-propanol. No exothermic reaction was observed. After addition, the reaction mixture was heated gradually to reflux at 85 C. Samples were withdrawn periodically for argentometric determination of ionic chloride forma tion.

The amination was discontinued in 10 hours time when no further increase of ionic chloride formation was observed. At this time, 138.0 g. 1.0 mole) of potassium carbonate slurried in g. of methanol were added to the reaction mixture to liberate the free amine. The prod; uct was recovered after the potassium chloride was filtered off and the solvents stripped under vacuum. Analysis 25 i 26 of the water-soluble and viscous product (saponification Company, Inc. (melt index 7.1, intrinsic viscosity 2.12, followed by argentometric titration) indicated that 85% and 94.2% isotactic) were spray-coated with 6% of the of the chloro sites in the halophosphonate were aminated. polyamino phosphonate prepared in Example 25 from a The final product may be represented by the formula benzene solution. The spray-coated pellets were first O CH3 0 dried at 65 C. in a draft oven for 15 minutes and were 11 u 5 H the d d 6 H2NECHECHZOP O CH P OUH I1(OCHZCHQNNH2)2 n me at 130 C for hours The dried and cooled coated pellets were spun at 260 C. at a screw pressure of 1500 p.s.i. The filament obtained was drawn and con- H H HQNNOHQ H2 CH3 CHZCHZNNHZ verted into a knitted fabric.

EXAMPLE 24 10 Samples of the knitted fabric were dyed with the fol- Preparation of a. polyamino phosphonate by amination of Iowmg dyes, together Wlfll ples from unmodified the halophosphonate of Formula 3 with dodecylamine Polypropylene filament- Into a three-necked flask equipped with a mechanical Eastman Blue BNN(C.I. Disperse Blue 3). stirrer, a thermometer, and a reflux condenser were Ea t ne Red B(C.I. Disperse Red 30).

charged 122.10 g. (0.20 mole) of the halogenated phos- (3) Polar Red 3B(Acid Red 134). a g g gi gi ;t i g g ggigg i ggg gg g g Eggs: While the knitted samples containing 6% polyamino panol. The reaction mixture was heated gradually to phosPhonate were dyed a bright shade with the afore reflux at Samples were withdrawn periodically rrenltlloned dyes, the untreated samples were not colored for argentometric titration of the formation of ionic a a EXAMPLE 27 chloride.

The amination was stopped when no further increase of ionic chloride formation was observed.

The aminated product was isolated after the inorganic Reaction of the halophosphonate of Formula 3 with polymeric Z-methylaziridine chloride formed was filtered off and the solvents were The halogenated phosphonate was gelled with polystripped under vacuum. The product was an oily viscous meric Z-methylaziridine into an insoluble film. The gelaliquid which was Water-insoluble but soluble in alcohols, tion was carried out according to the procedures of Exbenzene, chloroform and hexane. Analysis of the product ample 10 with the exception that methanol was used as (saponification followed by argentometric titration) in- 30 the diluent. The insolubilized materials were extracted dicated that the chloro sites in the halogenated phoswith benzene, methanol, water and then methanol. The phonate were fully arninated. The final product may be extracted materials were then dried in an oven at 150 C. represented by the formula to constant weight. The following results were obtained:

EXAMPLE 25 P t f Preparation of a polyamino phosphonate by amination polvm igri e Parts ofhaloiii s gl ifi li z of the halophosphonate of Formula 3 with octadecylmethylazmdme phosphonate tion amine 0. 47 1.0 65.0 Into a three-necked flask equipped with a mechanical 8-3; 1.0 51.6 stirrer, a thermometer, a reflux condenser were charged 61.05 g. (0.1 mole) of the halogenated phosphonate, 135.0 g. (0.5 mole) of octadecylamine, 69.0 g. (0.5 mole) of potassium carbonate and 300.0 g. of 2-propanol. The EXAMPLE 28 mixture was heated gradually to reflux at Q Samples Gelatlon of polyamino phosphonate with chlorosulfonated were withdrawn periodically for argentometric determina- 50 P y y n tion of ionic chloride. The amination was discontinued in 40 hours when no further increase of ionic chloride forwas gelled with hl lf t d polyethylene into an matron was observed. soluble elastic film. The chlorosulfonated polyethylene Th am Product Was fe'covered' as a Y sohd used was manufactured by E. I. du Pont de Nemours & 36 t0 after the morganlc mammals were Co. (Inc.) under the tradename Hypalon 20, the repeatfiltered off and the solvents were stripped otf under vaci i of h polymer having the foll wi approxillu Analysis Of the ProdllCt (Saponificatioll followed by mate structure, where p is the ratio of carbon-bound Cl argentometric titration) indicated that the chlorine atoms to lf b d C1; in the halogenated phosphonate were fully replaced. The aminated product, which was Water-insoluble but solu- The polyamino phosphonate prepared in Example 1 ble in alcohols, benzene, hexane and chloroform, may L J be represented by the formula 01501 01 EXAMPLE 26 The gelation was carried out according to the procedure Spinning of polypmpylene polyaminophoSphate mixture described in Example 10, except a methanol-toluene mixand dyeing of the filament obtained from the mixture ture was used as the diluent. The insolubilized materials Polypropylene peuets, 3 X 3 mm X 5 in obtained were extracted with toluene, acetone, water and size, sold under the trade name Escon 305 by Enjay then acetone. The extracted materials were then dried Parts of Parts of polyamino chlorosulionated yield of phosphonate polyethylene insolubilizatlon EXAMPLE 29 Preparation of a polyguanidino phosphonate by reaction of guanidine with the halophosphonate of Formula 3 01411280150 P 3 5H--NH C=NH 10 H Cl N Hz-H 01 (N eutralized wholly or in part by KzC O C19H4aN1aOnP =723 A polyguanidino phosphonate.

In a series of preparations in which the amounts of neutralizing base and solvent are varied, the following compounds are refluxed for 10 to days at 90 to 100 C 610 g. (1 mole) of an industrial grade of chlorinated phosphonate whose principal component (C H Cl O P has the type of structure shown in Formula 3;

478 g. (5 moles) of guanidine hydrochloride;

345 to 697 g. (2.5 to 5.0 moles) of potassium carbonate;

2 to 3 liters of 1-propanol; and 100 to 200 grams of water.

At the end of the refluxing period, conversions of 70 to 98% are shown by analysis of the supernatant liquid for chloride (bound as well as ionic). At this point, by-product potassium chloride and any residual ingredients are removed by filtration. That is followed by removal of solvents by distillation at reduced pressure until the remaining product weighs 750 to 820 grams. For complete replacement of chloro by guanidino, the theoretical yield would be 723 g. (1.0 mole), but that is not entirely achieved on the average. The product is amber-colored and water-soluble. For an evaluation of this product on cellulose-containing textile material, refer to Example 33.

Experience in several runs is that the resulting product has the following analysis:

Percent 5 C14H2s 5O0 3 0 28 EXAMPLE 30 Preparation of a polyureido phosphonate by reaction of urea with the halophosphonate of Formula 3 -5 H01 5H-NH C N H2 (Neutralized by K2 0 0 a) See Formula (3) O CHzCHzNHC ONHz The following compounds are heated at to C. for 7 days with agitation: 732 g. (1.2 moles) of an industrial grade of chlorinated phosphonate having the type of structure shown in Formula 3, 360 g. (7.8 moles) of urea, 414 g. (3.0 moles) of potassium canbonate, and 2.5 liters of bis(2-methoxyethyl) ether. Then an additional 50 g. (0.36 mole) of potassium carbonate and 50 g. 1.1 mole) of urea are added. The mixture becomes progressively more and more difficult to stir. After an additional day of stirring at 130 C., the supernatant liquid is removed by decantation. The residue is dissolved in hot methanol, is filtered, and the filtrate is mostly stripped of solvent leaving 830 grams of yellow viscous liquid. For complete replacement of chloro by ureido, the theoretical yield would be 728 grams for a solvent-free product of 100% purity.

Analysis.All of the N was of the amido type, inasmuch as titration of a sample with aqueous hydrochloric acid indicated the absence of amino N.

Required by Indicated Found CIVHMNWOHPQ P y N, percent 14. 53 i9. 22 75. 6 P, percent 9. 54 N atoms/P atom. 3. 37:1 Bound 01, percent 0. 42 Chloride ion, percent 0. 5

EXAMPLE 31 Poly-methylolation of a polyureido phosphonate by means of Formalin OCH2CHZNHCONH2 pH 9 to 9.5 IOOHgO O P CHzCHzNHC ONH2 CHP (:0)-O CHzGHzNHCONH:

H CH-P O)(O CH2OH2NHCONH2 2 0 CH2OHzN-C HzOH I =0 HN--CH2OH O P-CHzC HzN-CH2OH l :0 HN-CHzOH O GH-P (2O)OCH2CHzN-CH2OH HN-CHzOH O CH-P O) -OOH2OH2NOH2OH HNCH2OH A solution of 435 grams of the product of the preceding example and 375 grams of Water is adjusted to pH 9.5 with 6-normal sodium hydroxide. That solution is treated with 365 grams of 37% aqueous formaldehyde (4.5 moles), also previously adjusted to pH 9.5. The mixture is maintained at pH 9 to 9.5 for two 7-hour days of heating at 60 to 70 C., after which it is neutralized to pH 7. The resulting solution contains polymethylolated polyureido phosphonate. This solution is suitable for direct use to impregnate cellulose-containing textile material, as illustrated in Example 34.

ANALYSIS OF THE SOLUTION Any departure from the above description which conforms to the present invention is intended to be included within the scope of the invention.

What is claimed is:

1. A process for increasing the flame resistance of a polymeric material which comprises:

(1) applying to said polymeric material (a) tris(1-aziridinyl) phosphine oxide, and (b) a nitrogen-containing phosphonate compound N ff i obtained by reacting a halophosphonate selected P from the group wnsisting of Total formaldehyde (chromotropic acid proce- (H) dure) (ClCH2CH2O)zPCH2CHzCl Unbound formaldehyde (hydroxylamine hydrochloride procedure) 2.28 H 6 E 6 Bound N-hydroxymethyl groups (by difference) 5.93 (ClCHzCHzO)zPCHPO-CHP(O 01120151201 EXAMPLE 32 CH3 00112011201 Polymetholation of a polyureido phosphonate U (3H3 g by means of paraforrnaldehyde C10H2CH2O-POCHlrO-CHP(O CH2CH2Cl)2 A solution of 378 grams of the product of Example ClCHZ H2 omOCHQCHZCI 30 and 322 grams of water is heated with 123 grams of mom 0 CH3 0 95% paraformaldehyde (equivalent to 3.9 moles of form- E II l H aldehyde) at pH -8 to 9 for two 7-hour days at 60 to 70 CICHZ HTHOCHZCHCHZCD C. The resulting clear solution contains polymethylolated o r polyureido phosphonate capable of being reacted with (IJH2CHCHZC1 cellulosic hydroxyls through its N-hydroxymethyl groups. Br

ANALYSIS OF THE SOLUTION and derivatives of the above compounds wherein (Procedures as in Example 31) a portion of the chlorine atoms have been re- Percent placed by a phosphite radical of the formula Total formaldehyde 12.47 0 Unbound (free) formaldehyde 2:99 I! Bound N-hydroxymethyl groups 9.48 35 Pwmz EXAMPLE 33 where R is an alkyl group, with a nitrogen compound selected from the group consisting of am- Application of polyguanidino phosphonate to cotton twill o i hydr i e, alkyl di i f th Samples of 100% cotton fabric in a twill weave and formula weighing 8 ounces per square yard are conditioned at a NH C H NH relative humidity of 65% and are Weighed on an analytical balance. Then they are impregnated from pad bath h t a Is an Integer of from 2 to and alkyl' of various percentages of active reagent as shown in the emmme of the formula table. The solvent is water. The reagent is polyguanidino phosphonate, product of Example 29. The deposition is EN carried out on a laboratory padder so as to deposit ap- H proximately 3.0, 2.5, 2.0, 1.5, and 1% P, respectively, 2 in the fabric. The fabric samples so treated are dried at wherein R' is hydrogen or alkyl of from 1 to 4 about 65 C. and are not washed. Data are as follows: carbon atoms, and

Reagent, Wet Reagent, Char length, percent, on pickpercent, on Found, percent vertical wt. of 11 wt. of flame test, bath percent fabric P N inches Sample A 54 e3 34. 4 2. 99 7. 03 2. e B 40 61 24. 4 2. 36 6.35 2. 9 C 31 18. 6 1. 85 5. 26 a. 1 D 23 5e 12. 9 1. 45 4. 37 3. 5 E 16 52 s. 3 1. 02 3. 06 4. 9

EXAMPLE 34 (2) heating said polymeric material until said tris(1- aziridinyl) phosphine oxide and said nitrogen-contain- Apphcatlon of polyntlethoitatedt psllyureldo phosphonate ing phosphonate coreact to form an insoluble product 0 co on on said polymeric material. Samples of 100% cotton fabric in a twill weave and 65 2. A process as claimed in claim 1 wherein said polweighing 8 ounces per square yard are conditioned at a relative humidity of 65% and are weighed on an analytical balance. Then they are impregnated from a pad bath composed of the aqueous solution resulting from Example 31. The wet pick-up of the reagent, polymetholated polyureido phosphonate, is 68%. The actual weight gain is 25% on an oven-dry basis. Analytical determinations for deposited N and P show 1.93% and 1.91%, respectively. The fabric so treated is more flame retardant than untreated cotton fabric.

and said nitrogen compound reacted there-with is ethylene diamine.

31 4. A process as claimed in claim 1 wherein said halophosphonate has the formula u l H C1CH2CH2o-P0-CH-Po-bHP(oCHzCHzCI):

ClCHz H2 (EH3 CHzCHzCl and said nitrogen compound reacted therewith is ammonia.

5. A process as claimed in claim 1 wherein said halophosphonate has the formula II ll l n C1CH2CHzOPOCH-PO-CHP(OCHzCHzCDz 01011: H2 H3 dOHzCHzCl and said nitrogen compound reacted therewith is ethyleneimine.

6. A process as claimed in claim 1 wherein said nitrogen-containing phosphonate is prepared by reacting a compound of the formula with triethyl phosphite to replace a portion of the chlorine atoms with a radical of the formula and then reacting the resulting product with ethylene diamine.

7. A process as claimed in claim 1 wherein said tris(1- aziridynl) phosphine oxide and said nitrogen-containing phosphonate are applied to said polymeric material in an aqueous solution, following which the resulting product is dried and the tris(1-aziridynl) phosphine oxide and the nitrogen-containing phosphonate are coreacted by curing at a temperature of over 100 C.

8. A fire resistant polymeric material comprising a polymeric substrate impregnated with a flame retardant insoluble product formed by coreacting (a) tris(1-aziridinyl) phosphine oxide, and

(b) a nitrogen-containing phosphonate compound obtained by reacting a halophosphonate selected from the group consisting of BICH2 O CH; O

and derivatives of the above compounds wherein a portion of the chlorine atoms have been replaced by a phosphite radical of the formula where R is an alkyl group, with a nitrogen compound selected from the group consisting of ammonia, hydrazine, alkylene diamine of the formula 32 NH C H NH wherein a is an integer of from 2 to 6, and alkylenimine of the formula CHR CHz

wherein R is hydrogen or alkyl of from 1 to 4 carbon atoms 9. A flame resistant polymeric material as claimed in claim 8 wherein said polymeric substrate is cellulosic.

10. A flame resistant polymeric material as claimed in claim 8 wherein said halophosphonate has the formula n H CH3 u CICHzCHzO-POCHPO(HP(00112011701):

ClCHz H2 H5 OCHzCHzCl and the nitrogen compound reacted therewith is ethylene diamine.

11. A flame resistant polymeric material as claimed in claim 8 wherein said halophosphonate has the formula u ii CH3 I ClCHzOHzOP0CH1lO-('JH-l(O 0112011201 GIOHz H2 Ha OCHzCHzCl and the nitrogen compound reacted therewith is ammonia. 12. A flame resistant polymeric material as claimed in claim 8 wherein said halophosphonate has the formula M ii CH3 II O1CHzCHzOPOCHPO-( JHP(O CHZCHzCl):

ClCHzJJHz /Hg cHzcHlzol and the nitrogen compound reacted therewith is ethylenimine.

13. A flame resistant polymeric material as claimed in claim 8 wherein said nitrogen-containing phosphonate compound is prepared by reacting a halophosphonate of the formula 1 H ll ClCH2CH2Ol OCHlrOHP(O CHzCHzCDz 010112 H2 (BE, 00112011201 with triethyl phosphite to replace a portion of the chlorine atoms with a radical of the formula and then reacting the resulting product with ethylene diamine References Cited UNITED STATES PATENTS 2,681,920 6/1954 Van Winkle et al. 117136 X 3,146,228 8/1964 Chance 260239 3,188,341 6/1965 Smith et al. 117136 X 3,244,697 4/1966 Christena et al. 260-2 3,312,520 4/1967 Kenaga 117-136 X 3,381,063 4/1968 Zahir 260943 OTHER REFERENCES Drake et al.: APO, American Dyestutf Reporter, vol. 51, No. 8, pp. 40-42, Apr. 16, 1962.

WILLIAM D. MARTIN, Primary Examiner H. I. GWINNELL, Assistant Examiner US. Cl. X.R.

Patent N 3,516, 853 Dated June 23, 1970 and Kelvin B. Domovs Inventor(s) Giuliana C. Tesoro, Wing-Kai Lee,

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 2, line 60 (hydroxymethynamidino) should read (hydroxymethyl)amidino Column 5, lines 9 and 10 (2-chloroethyl) second occurrence should read 2- (chloroethyl) Column 6, line 74 A should read R Column 7, lines 12 and 13 "phosphoramidesipolyphosphonates" should read phosphoramidepolyphosphonates Column 8, line 9, COG should read COG 0 Column 9, Equation l2, line 20 ClCH CH O) 2 should read (CICHZCHZO) 2 ----7 Column 9, line 66, Formula 18 H-NC-NCH OH Should E O CH OH read H-N-C-N-CH OH E O CH OH Column 10, Formula 24, G-O-C-N-J should read GO-CNJ I I II I O CH OH O CH OH Column 13, line 9, "Tear strength ASTM D-l4l4-63" should read Tear strength ASTM D-l424-63 Column 15, line 60, "animation" should read amination FORM PO-IOSO (10'69) USCOMM-DC 0031 G-POG 0 I1. GOVIIIIIIT rllm'mc onlcl: u" (I-llI-SJA UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTIQN 2 Patent No. 3 516, 853 Dated June 23 1970 Inventor(s) Giuliana C Tesoro, Wing-Kai Lee and Kelvin B. Domovs It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 16, lines 5l 4, in the formula II: ll

V ll H N cH cH oP ocH should read |\1cH CH I NCH H2C FORM PC4050 (10-69 USCOMNFDC 0376-?89 I I... OVIIIIIIT IIIITIIG OIIIC! "(I o1n-w UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION 3 Patent No. 3'516'853 Dated June 23, 1970 1nventor(s) Giuliana C. Tesoro, Wing-Kai Lee, and Kelvin B. Domovs 5 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

- 9 5 3 Column 25, line 6, center of formula -cH I: OCH -P(OCH2 CH 0 CIi CI I E IIQPI 0 CH 0 I I 3 II should read CH P ocn P(OCH2 H CH OCH CH NNH Column 30, line 21, Claim 1, center of formula P O CH P O CH P (OCH should read l l I I I CICH CH CH2 OCH CH Cl o 0 CH 0 u n I II P O CH P O CH P (OCH CICH CH CH3 OCHZCHZC].

Column 31, lirme S5, Claim 8, left side of formula 0 O ClCH CH O-P should read C1CH CH2O-P ClCH CH O Signed and sealed this 17th day of Octooar 197 2.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. ROBERT GOTTSCH'ALK Attesting Officer Commissioner of Patents 

